Certain benzothiazolyl-coumarins

ABSTRACT

Dyes of the formula:

United States Patent Grau [ 1 Sept. 12, 1972 CERTAIN BENZOTHIAZOLYL-COUMARINS [72] Inventor: Gerhard Grau, l7 Kirchenstrasse,

6703, Limburgerhof, Germany [22] Filed: April 26, 1971 [2]] Appl. No,:137,681

30 Foreign Application Priority um I May 5, 1970 Germany ..P 20 21 899.9

[52] US. Cl. ..260/304, 260/37, 260/158,

260/240.l, 260/244 R, 260/247.1, 260/268 BC, 260/286, 260/293.67,260/294.8 C

Primary Examiner-Alex Mazel Assistant ExaminerR. J. GallagherAttomey-Johnston, Root, O'Keeffe, Keil, Thompso & Shurtleff [57]ABSTRACT Dyes of the formula:

@SOSX R J;

N /N \O 0 R2 especially in the form of the sodium, potassium or ammoniumsalts of the sulfonic acids. The dyes are particularly useful for dyeingsynthetic polyar mide textile materials.

2 Claims, No Drawings CERTAIN BENZOTHIAZOLYL-COUMARINS This inventionrelates to dyes of formula 1:

N l \N ivos/ in which R and R are identical or different and eachindividually stands for a methyl or ethyl group, or R and R togetherwith the nitrogen atom form the radical of a fiveor six-memberedheterocyclic ring, R stands for hydrogen, chlorine, bromine, methyl,ethyl, methoxy or ethoxy and X stands for hydrogen or a sodium orpotassium atom or a substituted or unsubstituted ammonium orcycloammonium radical.

Examples of fiveor six-membered heterocyclic rings which may be formedby R. and R together with the nitrogen atom are the radicals ofpyrrolidine, piperidine, piperazine and morpholine.

Ammonium or cycloammonium radicals carry a positive charge, which isnormally situated on the nitrogen atom but which may, due to mesomericstructures, be distributed in the molecule in some other way.Unsubstituted or substituted ammonium cations are preferred.

The ammonium ions are preferably derived from primary secondary ortertiary amines. Quaternary ammonium ions are also suitable. Othersuitable ammonium ions are cyclic ammonium ions, such as as pyridinium,quinolinimn, thiazolium and imidazolium ions.

' The unsubstituted or substituted ammonium cations preferably contain atotal of from four to 26 carbon atoms. I

Specific examples of the radical X are, apart from 20 hydrogen, sodiumand potassium:

(Hill (Hi3 CuHdClln)? COOCII;

CH3 CH5 CH3 CH1 Of particular commercial interest are the dyes of theformula la:

The new dyes may be manufactured by sulfonating the dyes free fromsulfonic acid groups and having the formula II:

in which R, R and R have the meanings stated above with respect toformula I.

Suitable sulfonating agents are the agents normally used for such apurpose, e.g., oleum containing from 5 to 50 percent of free sulfurtrioxide and chlorosulfonic acid.

When oleum is used sulfonation is advantageously carried out attemperatures between 5 and 100C and preferably between 30 and 60C,whilst in the case of chlorosulfonic acid temperatures between and 120Care used.

Where use is made of oleum having a concentrating of free sulfurtrioxide lower than 5 percent or of sulfur trioxide addition compoundssuch as piperidine chlorosulfonic acid, sulfonation only occurs at atemperature well above C.

The preparation of sulfonic acid salts is effectedby reacting thesulfonic acid in water and/or organic solvents with an equivalent ofsodium or potassium hydroxide or a nitrogen-containing organiccompounds, preferably an amine, advantageously dissolved in water or anorganic solvent or a mixture thereof.

An alternative method comprises the double reaction of an alkali metalsalt, for example the sodium salt, of the sulfonic acid with anequivalent amount of the nitrogen-containing organic compound in thepresence of water or an organic solvent or mixtures thereof.

Depending on its solubility in the diluent used, the salt with theorganic cation is completely or substantially precipitated and is thenisolated by filtration or it forms a solution, which is then evaporatedto dryness.

The novel dyes vary in color from red to yellow to green according tothe cation and have a high degree of brilliance. They are suitable forcoloring solvents, paints, coating compositions, textiles, paper andplastics. The novel dyes are particularly suitable for dyeing textilematerials of natural fibers and especially for dyeing synthetic fiberssuch as polyamides, of which nylon 6 and nylon 6.6 and'compounds ofsimilar structures may be specifically mentioned.

In the following Examples the parts are by weight unless otherwisestated.

EXAMPLE l SOzxH HaCz 70 parts of3-(benzthiazolyl-2)-7-diethylaminocoumarine are added to 700 parts of 10percent oleum within 1 hour at an internal temperature of from 5 to 10C.The dye passes into solution. The solution is dispersion. The freesulfonic acid is sparingly soluble in water. The free sulfonic acid issuspended in 700 parts of water and the suspension is adjusted to pH 8by adding 160 parts of 20% NaOH solution at from to C. On heating to60C, the free sulfonic acid passes into solution as the sodium salt. Tothe solution at 60C there are added 1,600 parts of saturated sodiumchloride solution to precipitate the sodium salt of 3-(benz-thiazolyl-2'-)-7-diethylaminocoumarine sulfonic acid. Afterfiltration, washing with common salt solution and drying at 70C, thereare obtained 105 parts of yellow dye.

EXAMPLE 2 1 so Na 1 8/ (C2I'I5)2N \O/-O parts of3-(benzthiazolyl-2'-)-7-diethylaminocoumarine are added to 350 parts ofchlorosulfonic acid within 1 hour at an internal temperature of 10C. Thedye passes into solution. The reaction mixtureis heated to 100C andstirred at this internal temperature for 4 hours. After cooling, themixture is poured onto ice and the precipitated sulfonyl chloride isfiltered off and washed with water. The moist filter cake is suspendedin 200 parts of water, and 24 parts of 50 percent sodium hydroxidesolution are added at from 90 to 100C. The resulting sodium salt of thesulfonic acid is precipitated by theaddition, at 60C, of saturatedsodium chloride solution. After filtration, washing with common saltsolution and drying at 70C, there are obtained 41 parts of yellow dye ofthe above formula.

EXAMPLE 3 EXAMPLE 4 e) l sol inncnn S/ ((321 [5)2N- 21 parts of3-(benzthiaz0lyl-2')-7-diethylaminocoumarine sulfonic acid are suspendedin 100 parts of ethanol, and 5 parts of n-butylamine are added at roomtemperature. The suspension is heated at from 60 to C, the resultingsalt of the sulfonic acid initially passing into solution for a shorttime before reprecipitating. The mixture is cooled and filtered. Thereare thus obtained 23 parts of yellow dye of the above structure.

-21 partsof 3-(benzthiazolyl-2f)J-diethylaminocoumarine sulfonicacid aresuspended in parts of ethanol, and 7 parts of cyclohexylamine are addedat room temperature-The suspension is, heated at from 60 to 70C, theresulting dye salt passing temporarily into solution. On cooling, thesalt is precipitated in a yellow crystalline form. It is filtered offand dried, and there are thus obtained 23 parts of dye.

EXAMPLE 6 43 parts of 3-(benzthiazolyl-2')-7-diethylaminocoumarinesulfonic acid are added in a finely divided state to 400 parts ofethanol to form a slurry, 40 parts of ethylhexoxypropylamine are addedat room temperature, and the suspension is heated at from 60 to 70C. Theresulting ammonium salt of the sulfonic acid passes into solution and itis necessary to evaporate the solution to dryness for its isolation.

EXAMPLE 7 H NR R is a mixture (C2115) 2N 01 0121125 to 01511 21 parts of3-(benzthiazolyl-2)-7-diethylaminocoumarine sulfonic acid are suspendedin 100 parts of dimethyl formamide, and a solution of 30 parts of afatty amine mixture (C to C in 100 parts of dimethyl formamide is addedat room temperature. The mixture is then heated at from 60 to 70C, andthe resulting ammonium salt immediately precipitates. The mixture iscooled to room temperature and filtered, and the solid residue is washedwith dimethyl formamide and water and dried at 70C to give 36 parts of ayellow dye salt of the above composition.

EXAMPLE 8 EXAMPLE 1 l N e e N s03 mN 11 l mat-3 l*\ 5 S (C1I:i)2N \O/:O

' e 0 20 parts of 3-(benzthiazolyl-2)-7- -1? Nnomfidimethylaminocoumarine sulfonic acid are added in a i finely dividedform to 200 parts of water to form a slurry, which is then heated atfrom 60 to 70C and adjusted to pH 8 by the addition of 5 parts ofpiperidine. The resulting solution is concentrated at subatmosphericpressure and the precipitate is filtered off and dried. There are thusobtained 25 parts of the yellow dye of the above structure. 22 parts ofthe dye 01. 45,160 are dissolved in 400 x I [P parts of water and mixedat room temperature, with a E LE 9 solution of 22 parts of the sodiumsalt of 3- (benzthiazolyl-2)-7-diethylaminocoumarine sulfonic H I QHEN/Q acid in 300 parts of water. The dye salt separates as a A dark redprecipitate and is filtered off and dried. It dyes organic solvents andplastics in fluorescent orange (Cz 5)2N 0 25 shades.

21 parts of 3-(benzthiazolyl-2')-7-diethylaminocou- EXAMPLE marinesulfonic acid are added in a finely divided state to 200 parts ofethanol to form a slurry, to which 5 N so 6 parts of morpholine areadded and, to ensure complete 1 a reaction, the mixture is heated atfrom 60 to 70C. The s resulting morpholinium salt passes into solutionfor a :0 short time and then separates out as a pale yellow finely 69divided precipitate. After filtering and drying, there are (c l mav- N(CH11): obtained 80 parts of the compound of the above struci ture.

| EXAMPLE 10 l l a N I V 1 S0 GH3N\@ /N CHE NllColls I \S/ 22 parts ofthe sodium salt of 3-(benzthiazolyl-2)-7- (02115) diethyl-aminocoumarinesulfonic acid are dissolved in 300 parts of water and combined, at roomtemperature, I with a solution of 28 parts of Victoria Blue B (C.l.Parts the sodlum Salt 0f 3-(benZth1aZ0lyl-2 44,045 in 12,00 parts ofwater. The precipitated dye diethyl-aminocoumarme sulfonic acid aredissolved in salt is filt d ff and dried at 0 Th h b- 200 parts of waterwith heating and the solution is m d 33 parts of d k green l cooled toroom temperature and mixed with a solution U i th d i ilar to thosedescribed in the 0f 12 Parts Of t ylpyridinium methosulfate in aboveExamples, further dyes having similar properties 50 parts of water. Theresulting solution is coneenare obtained using the sulfonic aciddescribed in Examtrated and the precipitated yellow dye salt is filteredoff ple 1 or its alkaline metal salts together with the comand dried.pounds indicated as cations in the following Table.

Shade of Example Cation resulting dye 13 (C1I3)4N@ Yellow. 14 alumna D0.

oimz wi omcdrt C5115 Ha -(5H2 Shade of Example Canon resulting dye 35(I) C 11 Grounl (C2H5)zN- N(CgI-15)z 36 C H Yellow.

G) HgN=l NH 37 e D0. CH2N|( 2 s)z 0 CH3 PAT N0 3, 691, 187 I, 867

C H3 N range (D 39 .e (CHz)zIIICHz-C5H5 Yellow.

a) 40 H3N(CHz)sN(CHs)2 41 HzN(C H9)g D0.

(9 42 HN(C4HQ)3 D0.

43 H H) D 4 2 44 mNomnzim) 02.

e 45 HaN C 11H33(l1) D0.

9 46 e. HnNCnHgfln) D0- 47 e e (CII3)3NCH2C&H5 DO- I claim: R is meth lor eth l and 1. A dye of the formula 2 y y X is hydrogen, sodium,potassium ammonium or substituted ammonium containing a total of fromfour to 26 carbon atoms.

2. A dye of the formula defined in claim 1, in which X is hydrogen,sodium, potassium, ammonium, iso-octylammonium oleylammonium,laurylammonium, din-butylammonium, di-isobutylammonium,cyclohexylammonium, dicyclohexylammonium, tributylammonium,phenylbenzyl-dimethylammonium, stearylbenzyl-dimethylammonium,benzyl-tri-methylammonium or dimethylaminopropylammonium.

mg I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,691, 187 Dated September 12, 9 2

Inventot(s) Gerhard 'Grau It is certified that: error appaars in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

. I "'3 Glover page, left hand column, insert [75] ASSIGNEE:

BadischeAni1in&Soda-Fabr1k Aktiengesellsohaft, Ludwigshafen am Rhein,Germany Column 5, line 58 odershould read or Signed and sealed this 13thday of March 1973.

(SEAL) Attest:

EDWARD I LFLETCHERJR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. A dye of the formula defined in claim 1, in which X is hydrogen,sodium, potassium, ammonium, ''''iso-octylammonium'''' oleylammonium,laurylammonium, di-n-butylammonium, di-isobutylammonium,cyclohexylammonium, dicyclohexylammonium, tributylammonium,phenylbenzyl-dimethylammonium, stearylbenzyl-dimethylammonium,benzyl-tri-''''methylammonium'''' or dimethylaminopropylammonium.